Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix
Nanoparticles ZnO:Mn (3–5nm) immobilized in polyethylene matrix were synthesized. The samples with different content of the manganese (5, 10 and 20%) in the initial solution of the Mn and Zn precursors were investigated by means of ESR, PL and XRD. Thus the behavior of the Mn impurities in ZnO was s...
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Інститут проблем матеріалознавства ім. І.М. Францевича НАН України
2010
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| Zitieren: | Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix / G.V. Lashkarev, P.V. Demydiuk, G.Yu. Yurkov, O.I. Dmitriev, O.I. Bykov, L.I. Klochkov, Y.P. Pyratinskiy, E.I. Slynko, A.G. Khandozhko, O.V. Popkov, N.A. Taratanov // Наноструктурное материаловедение. — 2010. — № 4. — С. 3-9. — Бібліогр.: 13 назв. — англ. |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1859649886955241472 |
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| author | Lashkarev, G.V. Demydiuk, P.V. Yurkov, G.Yu. Dmitriev, O.I. Bykov, O.I. Klochkov, L.I. Pyratinskiy, Y.P. Slynko, E.I. Khandozhko, A.G. Popkov, O.V. Taratanov, N.A. |
| author_facet | Lashkarev, G.V. Demydiuk, P.V. Yurkov, G.Yu. Dmitriev, O.I. Bykov, O.I. Klochkov, L.I. Pyratinskiy, Y.P. Slynko, E.I. Khandozhko, A.G. Popkov, O.V. Taratanov, N.A. |
| citation_txt | Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix / G.V. Lashkarev, P.V. Demydiuk, G.Yu. Yurkov, O.I. Dmitriev, O.I. Bykov, L.I. Klochkov, Y.P. Pyratinskiy, E.I. Slynko, A.G. Khandozhko, O.V. Popkov, N.A. Taratanov // Наноструктурное материаловедение. — 2010. — № 4. — С. 3-9. — Бібліогр.: 13 назв. — англ. |
| collection | DSpace DC |
| container_title | Наноструктурное материаловедение |
| description | Nanoparticles ZnO:Mn (3–5nm) immobilized in polyethylene matrix were synthesized. The samples with different content of the manganese (5, 10 and 20%) in the initial solution of the Mn and Zn precursors were investigated by means of ESR, PL and XRD. Thus the behavior of the Mn impurities in ZnO was studied. It was observed that most of the manganese in ZnO form second undefined phase MnOx or substitute the zinc in cation sublattice at the surface layer of the nanoparticles. The mean value of constant of hyperfine structure of Mn is higher than expected one (<A> = (94±3)·10⁻⁴ cm⁻¹) that is significantly differ from the constant of hyperfine structure of Mn incorporated into single crystal ZnO (76·10⁻⁴ cm⁻¹). Photoluminescence measurements has revealed wide band of emission in green-red region 500–600 nm, with different position of the maximum depending on the manganese content.
Отримано наночастинки ZnO:Mn розміром 3–5 нм. За допо-могою методів ЕПР, рентгеноструктурного аналізу та фотолюмінесценції досліджували структуру цих наночастинок із вмістом марганцю 5, 10 і 20% щодо вихідного розчину пре-курсорів. Показано, що переважна кількість марганцю формує другу фазу та заміщує цинк у катіонній підрешітці вповерхневому прошарку цих наночастинок. Середнє значення константи надтонкої структури (<A> = (94±3)·10⁻⁴ см⁻¹),отримане методом ЕПР, виявилося більшим за очікуване та відмінним від довідникового для марганцю в кристалічній решітці ZnO (76·10⁻⁴ см⁻¹). Фотолюмінесцентні вимірювання виявили широку лінію випромінювання в зелено-червоній області спектра 500–600 нм із різним положенням максимуму залежно від типу зразка.
Получены наночастицы ZnO:Mn размером 3–5 нм. С помощью методов ЭПР, рентгеноструктурного анализа и фотолюминесценции исследовалась структура этих наночастиц с содержанием марганца 5, 10 и 20% относительноисходного раствора прекурсоров. Показано, что преимущественное количество марганца формирует вторую фазу и замещает цинк в катионной подрешетке в поверхностномслое этих наночастиц. Среднее значение константы сверхтонкой структуры (<A> = (94±3)·10⁻⁴ cm⁻¹), полученное методомЭПР, оказалось большим по сравнению с ожидаемым и отличным от справочного для марганца в кристаллической решетке ZnO (76·10⁻⁴ см⁻¹). Фотолюминесцентные измерения выявили широкую линию излучения в зелено-красной области спектра 500600 нм с разным положением максимума в зависимости от типа образца.
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 4
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ,
ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
G.V. Lashkarev1, P.V. Demydiuk1, G.Yu. Yurkov2, O.I. Dmitriev1,
O.I. Bykov1, L.I. Klochkov1, Y.P. Pyratinskiy3, E.I. Slynko1,
A.G. Khandozhko4, O.V. Popkov2, N.A. Taratanov2
1Frantsevich Institute for Problems of Material Science, National Academy of Science of Ukraine
Krzhyzhanovsky str., 3, Kiev, 03142, Ukraine
2A.A. Baikov Institute of Metallurgy and Materials Science of Russian academy of science
Leninsky prospect, 49, Moscow, 119991, Russia
3Institute of Physics, National Academy of Science of Ukraine
Prospect Nauky, 46, Kiev, 03650, Ukraine
4Yuriy Fedkovich Chernivtsi National University
Kotsiubynskogo str., 2, Chernivtsi, 58012, Ukraine
PROPERTIES OF NANOPARTICLES ZnO:Mn
IMMOBILIZED IN POLYETHYLENE MATRIX
Key words: nanoparticle, ZnO, Mn,
photoluminescence, luminescence,
ESR
ÓÄÊ 538.9
Nanoparticles ZnO:Mn (3–5nm) immobilized in polyethylene matrix were synthesized.
The samples with different content of the manganese (5, 10 and 20%) in the initial solution
of the Mn and Zn precursors were investigated by means of ESR, PL and XRD. Thus the
behavior of the Mn impurities in ZnO was studied. It was observed that most of the
manganese in ZnO form second undefined phase MnOx or substitute the zinc in cation
sublattice at the surface layer of the nanoparticles. The mean value of constant of hyperfine
structure of Mn is higher than expected one (<A> = (94±3)·10–4 cm–1) that is significantly
differ from the constant of hyperfine structure of Mn incorporated into single crystal ZnO
(76·10–4 cm–1). Photoluminescence measurements has revealed wide band of emission in
green-red region 500–600 nm, with different position of the maximum depending on the
manganese content.
Introduction
Onrush of nanotechnology gives rise to reconsideration of functional
capacity of well-known materials. In particular many papers have been
dedicated to the research on nanosized systems that are based on zinc oxide.
ZnO is a direct wide-gap (3.37 eV) semiconductor with extremely high
exciton binding energy (60 meV). In addition it is nonexpensive, nontoxic and
G.V. LASHKAREV, P.V. DEMYDIUK,
G.YU. YURKOV, O.I. DMITRIEV,
O.I. BYKOV, L.I. KLOCHKOV,
Y.P. PYRATINSKIY, E.I. SLYNKO,
A.G. KHANDOZHKO, O.V. POPKOV,
N.A. TARATANOV, 2010
©
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 4
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ, ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
resistive to the high energy radiation [1]. These features
should create prerequisites for ZnO to be applied in
crystalophosphors as work medium for luminescent
centers. Quantitative characteristics of such optical
system are altered with transition to nanoscale as a
result of profound influence of confinement effects
and surface states. The former is based on effect of
surface restriction that in turn acts as potential barrier
with endless walls.
As a result, confinement effect leads to increasing
of band gap, binding energy of exciton and
overlapping of electron-hole wave functions. Each
mentioned effect makes its positive contribution to
quantum efficiency of the crystalophosphors what
consists in increasing of oscillator strength of band-
to-band transition, lifetime of exciton and probability
of their interaction with luminescent centers [2].
In order to research such system, nanoparticles (NP)
ZnO:Mn2+ immobilized in polyethylene matrix (hereafter
Samples) were synthesized. Manganese is expected
to be center of yellow-green luminescence (~580 nm)
due to 4T1(G) – 6A1 transition in crystal field of
hexagonal symmetry [3] (for example ZnS). Moreover
orbital and spin quantum numbers of Mn2+ in ground
state are L = 0 and S = 5/2. Therefore it is also proper
element for probing of local surroundings in the host
by means of ESR (Mn2+ has six lines of hyperfine
structure). That is very important upon studying of
doped nanoparticles.
As for the synthesis process the mixture of
precursors containing Zn2+ and Mn2+ ions was
introduced into the solution of polyethylene in
hydrocarbon oil. Thus separated particles were
protected from agglomeration and atmospheric impact.
It was also observed that behavior of the NP had been
correlated by option of zinc and manganese precursors.
Therefore influence of mixtures of precursors
Zn(NO3)2 with Mn(NO3)2 and Zn(CH3COO)2 with
Mn(CH3COO)2 on the NP properties was studied.
Experement
Synthesis
Investigated NPs were synthesized in compliance
with the methodology that was described elsew-
here [4, 5]. A water solution of Zn and Mn precursors
with the concentration varying from 0.05 to 0.06 mol/l
was prepared. LDPE (low density polyethylene) was
dissolved in mineral oil in argon atmosphere using
intensive stirring and heating. A solution of precursors
was being introduced dropwise into the reaction mass
for 24 h at 250 °C. Throughout a synthesis, gaseous
products of the reaction and residual water were
removed from the reaction vessel by an argon
stream. Afterwards, a reaction mass (polymer-
nanoparticles-oil) was stirred at a proper temperature
for 40 min with the purpose to complete thermal
decomposition of the initial precursors, then cooled
down to room temperature and placed into a Soxhlet
extractor where residual oil was completely removed.
Two groups of Samples were prepared.
Zn(NO3)2 with Mn(NO3)2 and Zn(CH3COO)2 with
Mn(CH3COO)2 were used as the zinc and man-
ganese precursors for preparation of the first and
second groups of samples, respectively. Three types
of Samples that were synthesized from initial
solution of precursors containing 5, 10, and 20 %wt.
of Mn were studied in both groups (Table 1).
However the initial solution of the precursors
consists of particular amount of the manganese, its
actual concentration in final nanoparticles ZnO is
under question and may strongly diverge from the
initial value. Within this paper it is considered that
value of the manganese concentration in nano-
particles ZnO is less than 1%. This assumption is
made on the base of ESR measurements, that have
shown six line of the hyperfine structure (Fig. 5),
that means low amount (<1%) of magnetic ions
have been introduced into the nanoparticles ZnO.
As for the localization of the rest part of manganese
it seems to form some oxygen phase MnOx. Its
presence is indicated by X-ray diffraction measu-
rement (Fig. 2 the band under notation MnOx).
Measurement equipment
X-ray diffraction measurements (XRD) were
performed with modified computer-controlled
diffractometer DRON-3M equipped with X-ray
tube BSV-28, cupper anode (λ = 1.54 µkm) and
nickel filter. Data processing was performed
according to the database of standard XRD
spectrum value ASTM (American Society of
Testing Materials).
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 4
Photoluminescence (PL) spectra were excited
by nitrogen laser (337 nm) and measured at room
temperature.
Results and discussion
Six Samples were synthesized (Òable 1). The
average size of NP was estimated using TEM
instrument (Fig. 1) and assigned to be 3–5 nm.
Basing on minimum energy principle for surface
strain and TEM image (Fig.1) the NPs are
suggested to have sphere like shape.
The XRD pattern exhibited a wurtzite structure
of ZnO (Fig. 2), for both groups of Samples. Two
Samples with the highest content of manganese
(20%) from every of the groups (N3 and N6) and
one Sample N1 (5% Mn) were chosen to compare
with one another. As it can be seen from Fig. 2 they
have particularly identical XRD spectra that are
characterized by six lines of ZnO hexagonal structure
and weak unidentified lines with 2θ = 38÷49°.
According to the ASTM these unknown lines can be
assigned to be compounds of manganese with
oxygen. Thus we could hardly give unambiguous
answer what these phases are, so hereinafter they
are referred as MnOx (Manganese oxide).
A comparative analysis of XRD spectra for N1,
N3 and N6 was performed. To reveal difference
between these Samples, two parameters for each
spectrum were estimated. First parameter is a
interplanar spacing of crystalline structures,
calculated by Bragg’s equation (Fig. 3):
(1)
Second parameter is a relative size of coherent
scattering region (CSR), calculated on the basis of
Debai–Sherrer equation (Òable 2):
(2)
Table 1. List of synthesized Samples
Fig. 2. XRD spectrum for Samples N1, N3, N6
300
200
100
0
25 30 35 40 45 50 55 60 65 70
2θ
I (a.u.)
(1
00
)
(0
02
)
(1
01
)
(1
10
)
(1
03
)
(1
12
)
MnOX
N6
N3
N1
Fig. 1. TEM image of ZnO:Mn nanoparticles. The average
size of the NP is 3–5 nm
10 nm
The ESR experiments were performed at X band
~10 GHz at room temperature.
·
·
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 4
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ, ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
This parameter in contrast to the first one
depends on FWHM of the XRD spectra lines and
is used to estimate comparative characteristic (not
absolute) of coherent scattering region of the
nanoparticles. FWHM have been calculated as full
width at half maximum on Gauss curve that
approximate the XRD spectrum lines.
In both equations (1) and (2) the notation θ and
stands for the scattering angle and wave length
1.54 mkm, respectively.
One can see (Fig. 3) that interplanar spacing of
crystalline lattice of ZnO nanoparticles in Sample N1
(5% Mn) are slightly shifted to the lower values in
comparison with the ones for N3, N6 and ASTM. Since
the nanoparticles contain low amount of the mangane-
se (<1%) thus it hardly could change the lattice parameters
of ZnO because of bigger ion radii of Mn+2 (0.8 nm)
opposite to the ion radii Zn2+ (0.73 nm). However such
behavior can be explained if we take into account an
effect of surface tension on periods of the crystalline
structure. For nanoparticles where surface to volume
ratio is high, crystalline structure is strongly affected by
surface tension that results in decreasing of the periods
of the crystalline lattice. In addition the dimension of the
coherent scattering region (Òable 2) for these three
Samples has similar dependence except for the (002)
case. Thus basing on these facts we can assume that
average size of NPs ZnO:Mn N1 is smaller than
NP N3 and N6.
ESR measurements
Due to half-filled d shell (3d5) with spin S = 5/2,
angular momentum L = 0 and nucleus spin I = 5/2,
the resonance of an isolated Mn2+ ion located
substitutionally on a Zn site in hexagonal ZnO is
described by the spin Hamiltonian:
(3)
At low concentration (<0.1%) Mn doped ZnO
single crystals, an isotropic Zeeman (first term eq. 3)
and hyperfine interaction (second term eq. 3) were
observed (g = 2.0016, |A| = 76·10–4 cm–1) together
with an axial fine structure splitting (D = 217·
·10–4 cm–1) [6]. In the case of randomly oriented
nanocrystals anisotropic contributions are washed
out and one can expect a six line spectrum with
a hyperfine splitting (hereafter HFS) of about
76·10–4 cm–1 from isolated Mn2+ incorporated in the
single crystal ZnO.
ESR measurements were used to investigate a
behavior of Mn2+ in the host material ZnO. ESR
spectrums for five Samples are given on Fig. 5. It
shall be noted that ESR spectra for Samples N1 is
not resolved thus it is not given in this article.
According to these measurements two spectrum
patterns can be highlighted:
S1 – broad background line that inhere for all ESR
spectrums (dash-dotted lines on the Fig. 5) is related
to the exchange and dipole-dipole interaction of Mn
between nearby magnetic centers. This line can be
attributed to the unknown phase MnOx (Fig. 2);
S2 – six lined hyperfine structure with mean
constant of HFS (CHFS) <A> = (94±3)·10–4 cm–1
is related to the isolated Mn in ZnO lattice. Value
Table 2. Relative value of coherent scattering region of
three Samples N1, N3 and N6 calculated by equation (2)
Fig. 3. comparative values of interplanar spacing of
Samples N1, N3, N6 and corresponding ASTM value for
three different directions
2,80
2,75
2,70
2,65
2,60
2,55
2,50
2,45
Samples
d (angstrem)
N3
N1
N6 ASTM
N3
N1
N6 ASTM
N3
N1
N6 ASTM
(100)
(001)
(101)
μ
7
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 4
of the constant of HFS is given as «almost equal»
because it is mean value over all six lines. Detailed
estimation of this value gives confidence interval
as ±3. However it is crude approximation but for
our objectives and conclusion it is enough.
In hexagonal ZnO lattice manganese ions that
substitute of Zn2+ in the single crystal undergo the
effect of tetrahedral electrostatic field of the
surroundings. In such a case the CHFS of Mn2+ is
76·10–4 cm–1, in contrast to observed HFS of Mn in
ZnO nanoparticles with considerably higher CHFS
(<A> = (94±3)·10–4 cm–1).
a
Fig. 4. PL spectra for Samples (a) N1–3 and (b) N4–6.
b
1,0
0,8
0,6
0,4
0,2
3000 3600 4200
H (Gs)
3
2
1
0
–1
0,4
0,2
0,0
–0,2
–0,4
–0,6
1,0
0,5
0,0
–0,5
1,4
1,2
1,0
0,8
0,6
0,4
3000 3600 4200
I(
N
2)
I(
N
3)
I(
N
4)
I(
N
5)
I(
N
6)
Fig. 5. ESR spectrum for (a) Samples N2–6 at T = 300 K
400 450 500 550 600 650 700 750 800
λ
PL intensity (a. u.)
λmax(N3) = 596 nm
N3
N2
N1
400 450 500 550 600 650 700 750 800
λ
PL intensity (a. u.)
λmax(N6) = 556 nm
λmax(N5) = 560 nm
λmax(N4) = 587 nm
N6
N5
N4
Similar increasing of CHFS for manganese in
hexagonal lattice has been observed earlier in
nanopowders CdS, ZnS [7–9] and ZnO [10]
synthesized in colloidal solution. Such increasing in these
works related to formation of cubic Zn(OH)2 crystalline
phase on the surface of the nanoparticles. In this
structure Mn2+ can substitute zinc ions in octahedral
surrounding of hydroxide groups. But in our work the
synthesis was held under such conditions that exclude
formation of any compounds except ZnO and
manganese oxides. Thus explanation of such value of
CHFS can be related to the disturbances of tetrahedral
Zn sublattice at the surface layer of ZnO and formation
of octahedral surrounding around manganese ions.
This conclusion is based on the fact that CHFS of
Mn in tetrahedral surrounding has lower value than in
the case of octahedral one (Òable 3). As it can be seen
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 4
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ, ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
from the table CHFS <A> = (94±3)·10–4 cm–1 lay in
the range of the values for octahedral local environment.
These two spectra S1 and S2 are more or less
detected for investigated Samples N2–6. In particu-
lar S1 ESR signal is well observed for whole number of
Samples that indicate second phase formation (com-
pound with Mn component) for all of them. Sextet
structure S2 is weakly resolved for members
of second group (N4–6) but nearly absent for Samples
N1 and N2. The difference between these two groups
lays in type of Zn and Mn precursors that are used in
chemical synthesis reaction. From this point of view
manganese, that is easily oxidized metal, differently acts
in nitride and acetate solutions [3]. In second group of
precursors the Mn oxidation is more inhibited than in
nitrides solution. That leads to increasing of second phase
formation in the last medium in comparison with the
first one. Therefore one can observe more intensive six
lined structure for N4 and N5 than for N1 and N2.
Photoluminescent spectrum
The PL spectrum of bulk ZnO is characterized by
two lines. First one lays in UV region 350–370 nm
and attributed to the near band gap exciton
recombination PL. Second one, wide band line, lies
in green-red region of the visible spectrum (500–
600 nm) and caused by intrinsic point defects within
zinc oxide that lead to appearing of deep and shallow
defects levels in the band gap [12–13].
At the transition to nanosized objects the PL
spectrum become more ambiguous than in the bulk case.
Since influence of surface layer states in such entities is
significantly enhanced with decreasing of their size. Thus
it is expected to observe additional lines in the spectrum
of nano ZnO attributed to the surface layer. The lines
can be varied depending on the shape of the nanoparticles.
On the Fig. 4 spectra of nanoparticles ZnO doped
with Mn are shown. All Samples are characterized by
UV component (~370 nm) that is poor resolved on the
UV band of nitrogen laser background (this line is not
shown on the pictures). In addition wide band in visible
region of the spectrum (500–600 nm) is observed too.
The significant widening of this line is clearly attributed
to wide distribution of the emission spectrum of the
individual nanoparticle within any of the Samples.
Characteristic dimensions of these nanoparticles is
decreased enough that their shape and dimensions have
significant influence on the optical transitions.
For the Samples N1–2 the intensity of the lines in
visible region lies at the noise level. In these nanoparticles
the radiationless transition is dominated. But as for the
Samples with higher manganese content there is
intensive line of emission centered at the 590 nm
(Fig. 4a). Similar picture is observed for Samples N4–6,
the Samples with the highest manganese content show
the most intensive line in the visible region (Fig. 4b).
There is not enough information to definitely conclude
about origin of these lines, but some assumption can be
made. Whereas the band line strongly overlap region of
defect emission that attributed to the native point defects
in ZnO [12], we can make assumption that one of the
sources of the green emission is these point defects.
That is even in the Samples N1–2 there are low resolved
picks in 530 nm. Other sources of the emission are
assumed to be surface states that depend on manganese
content at the surface layer of the nanoparticles.
Absence of the isolate manganese in the Samples N1–
2 is also confirmed by ESR measurements. For other
Samples where isolate manganese was found by ESR,
the PL spectrum have been observed. Therefore we
can assume that manganese ions participate in forming
or modification of the ZnO defects on the surface level
and in some way promote emission in visible region of
the spectrum.
The role of the manganese as surface agent, but
not luminescence center itself is proved by different
position of the PL lines for the Samples with different
manganese contents. However luminescence of the
manganese (580 nm) could not be eliminated.
Table 3. Comparative table of constants of hyperfine
structure for Mn in local octahedral and tetrahedral
surrounding
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Conclusions
Within this work nanoparticles ZnO doped with
Mn immobilized in polyethylene matrix with
average size 3–5 nm were synthesized. Two
different localizations of Mn have been revealed.
First one is localization at the surface layer
substituting zinc in cation sublattice (<A> =
= (94±3)·10–4 cm–1) that differ from constant of
hyperfine structure for ZnO 76·10–4 cm–1. The
second one is thought to form undefined phase
MnOx with unresolved hyperfine structure. Under
nitrogen laser excitation (337 nm) visible emission
in the range 500–600 nm has been observed that
is attributed to defect surface states that are
predominant in the nanoparticles.
This work was financed by the Russian Foundation
for Basic Research (grant nos. 10-08-90421-Óêð and
10-03-00466-a) and the grant of the President of the
Russian Federation MD-5551.2010.3.
Îòðèìàíî íàíî÷àñòèíêè ZnO:Mn ðîçì³ðîì 3–5 íì. Çà äîïî-
ìîãîþ ìåòîä³â ÅÏÐ, ðåíòãåíîñòðóêòóðíîãî àíàë³çó òà ôîòî-
ëþì³íåñöåíö³¿ äîñë³äæóâàëè ñòðóêòóðó öèõ íàíî÷àñòèíîê ³ç
âì³ñòîì ìàðãàíöþ 5, 10 ³ 20% ùîäî âèõ³äíîãî ðîç÷èíó ïðå-
êóðñîð³â. Ïîêàçàíî, ùî ïåðåâàæíà ê³ëüê³ñòü ìàðãàíöþ ôîð-
ìóº äðóãó ôàçó òà çàì³ùóº öèíê ó êàò³îíí³é ï³äðåø³òö³ â
ïîâåðõíåâîìó ïðîøàðêó öèõ íàíî÷àñòèíîê. Ñåðåäíº çíà÷åí-
íÿ êîíñòàíòè íàäòîíêî¿ ñòðóêòóðè (<A> = (94±3)·10–4 ñì–1),
îòðèìàíå ìåòîäîì ÅÏÐ, âèÿâèëîñÿ á³ëüøèì çà î÷³êóâàíå òà
â³äì³ííèì â³ä äîâ³äíèêîâîãî äëÿ ìàðãàíöþ â êðèñòàë³÷í³é
ðåø³òö³ ZnO (76·10–4 ñì–1). Ôîòîëþì³íåñöåíòí³ âèì³ðþâàí-
íÿ âèÿâèëè øèðîêó ë³í³þ âèïðîì³íþâàííÿ â çåëåíî-÷åð-
âîí³é îáëàñò³ ñïåêòðà 500–600 íì ³ç ð³çíèì ïîëîæåííÿì ìàê-
ñèìóìó çàëåæíî â³ä òèïó çðàçêà.
Êëþ÷îâ³ ñëîâà: íàíî÷àñòèíêà, ZnO, Mn, ôîòîëþì³íåñ-
öåíö³ÿ, ëþì³íåñöåíö³ÿ, ÅÏÐ
Ïîëó÷åíû íàíî÷àñòèöû ZnO:Mn ðàçìåðîì 3–5 íì. Ñ ïî-
ìîùüþ ìåòîäîâ ÝÏÐ, ðåíòãåíîñòðóêòóðíîãî àíàëèçà è
ôîòîëþìèíåñöåíöèè èññëåäîâàëàñü ñòðóêòóðà ýòèõ íàíî-
÷àñòèö ñ ñîäåðæàíèåì ìàðãàíöà 5, 10 è 20% îòíîñèòåëüíî
èñõîäíîãî ðàñòâîðà ïðåêóðñîðîâ. Ïîêàçàíî, ÷òî ïðåèìó-
ùåñòâåííîå êîëè÷åñòâî ìàðãàíöà ôîðìèðóåò âòîðóþ ôàçó
è çàìåùàåò öèíê â êàòèîííîé ïîäðåøåòêå â ïîâåðõíîñòíîì
ñëîå ýòèõ íàíî÷àñòèö. Ñðåäíåå çíà÷åíèå êîíñòàíòû ñâåðõòîí-
êîé ñòðóêòóðû (<A> = (94±3)·10–4 cm–1), ïîëó÷åííîå ìåòîäîì
ÝÏÐ, îêàçàëîñü áîëüøèì ïî ñðàâíåíèþ ñ îæèäàåìûì è
îòëè÷íûì îò ñïðàâî÷íîãî äëÿ ìàðãàíöà â êðèñòàëëè÷åñêîé
ðåøåòêå ZnO (76·10–4 ñì–1). Ôîòîëþìèíåñöåíòíûå èçìåðå-
íèÿ âûÿâèëè øèðîêóþ ëèíèþ èçëó÷åíèÿ â çåëåíî-êðàñ-
íîé îáëàñòè ñïåêòðà 500–600 íì ñ ðàçíûì ïîëîæåíèåì ìàê-
ñèìóìà â çàâèñèìîñòè îò òèïà îáðàçöà.
Êëþ÷åâûå ñëîâà: íàíî÷àñòèöà, ZnO, Mn, ôîòîëþìèíåñ-
öåíöèÿ, ëþìèíåñöåíöèÿ, ÝÏÐ
1. Klingshirn C.F. ZnO: From basics towards applications //
Phys. Stat. Sol. B. – 2007. – 244, N 9. – P. 3027–3073.
2. Bryan J.D., Gamelin D.R. Doped semiconductor
nanocrystals: synthesis, characterization, physical
properties and applications // Progress in Inorganic
Chemistry – John Wiley & Sons, Inc. – 2005, Vol. 54,
pp. 47–126.
3. Synthesis of colloidal Mn2+:ZnO quantum dots and High-
TC ferromagnetic nanocrystalline thin films / Norberg N.S.,
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| id | nasplib_isofts_kiev_ua-123456789-62735 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1996-9988 |
| language | Russian |
| last_indexed | 2025-12-07T13:32:30Z |
| publishDate | 2010 |
| publisher | Інститут проблем матеріалознавства ім. І.М. Францевича НАН України |
| record_format | dspace |
| spelling | Lashkarev, G.V. Demydiuk, P.V. Yurkov, G.Yu. Dmitriev, O.I. Bykov, O.I. Klochkov, L.I. Pyratinskiy, Y.P. Slynko, E.I. Khandozhko, A.G. Popkov, O.V. Taratanov, N.A. 2014-05-25T11:42:20Z 2014-05-25T11:42:20Z 2010 Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix / G.V. Lashkarev, P.V. Demydiuk, G.Yu. Yurkov, O.I. Dmitriev, O.I. Bykov, L.I. Klochkov, Y.P. Pyratinskiy, E.I. Slynko, A.G. Khandozhko, O.V. Popkov, N.A. Taratanov // Наноструктурное материаловедение. — 2010. — № 4. — С. 3-9. — Бібліогр.: 13 назв. — англ. 1996-9988 https://nasplib.isofts.kiev.ua/handle/123456789/62735 538.9 Nanoparticles ZnO:Mn (3–5nm) immobilized in polyethylene matrix were synthesized. The samples with different content of the manganese (5, 10 and 20%) in the initial solution of the Mn and Zn precursors were investigated by means of ESR, PL and XRD. Thus the behavior of the Mn impurities in ZnO was studied. It was observed that most of the manganese in ZnO form second undefined phase MnOx or substitute the zinc in cation sublattice at the surface layer of the nanoparticles. The mean value of constant of hyperfine structure of Mn is higher than expected one (<A> = (94±3)·10⁻⁴ cm⁻¹) that is significantly differ from the constant of hyperfine structure of Mn incorporated into single crystal ZnO (76·10⁻⁴ cm⁻¹). Photoluminescence measurements has revealed wide band of emission in green-red region 500–600 nm, with different position of the maximum depending on the manganese content. Отримано наночастинки ZnO:Mn розміром 3–5 нм. За допо-могою методів ЕПР, рентгеноструктурного аналізу та фотолюмінесценції досліджували структуру цих наночастинок із вмістом марганцю 5, 10 і 20% щодо вихідного розчину пре-курсорів. Показано, що переважна кількість марганцю формує другу фазу та заміщує цинк у катіонній підрешітці вповерхневому прошарку цих наночастинок. Середнє значення константи надтонкої структури (<A> = (94±3)·10⁻⁴ см⁻¹),отримане методом ЕПР, виявилося більшим за очікуване та відмінним від довідникового для марганцю в кристалічній решітці ZnO (76·10⁻⁴ см⁻¹). Фотолюмінесцентні вимірювання виявили широку лінію випромінювання в зелено-червоній області спектра 500–600 нм із різним положенням максимуму залежно від типу зразка. Получены наночастицы ZnO:Mn размером 3–5 нм. С помощью методов ЭПР, рентгеноструктурного анализа и фотолюминесценции исследовалась структура этих наночастиц с содержанием марганца 5, 10 и 20% относительноисходного раствора прекурсоров. Показано, что преимущественное количество марганца формирует вторую фазу и замещает цинк в катионной подрешетке в поверхностномслое этих наночастиц. Среднее значение константы сверхтонкой структуры (<A> = (94±3)·10⁻⁴ cm⁻¹), полученное методомЭПР, оказалось большим по сравнению с ожидаемым и отличным от справочного для марганца в кристаллической решетке ZnO (76·10⁻⁴ см⁻¹). Фотолюминесцентные измерения выявили широкую линию излучения в зелено-красной области спектра 500600 нм с разным положением максимума в зависимости от типа образца. This work was financed by the Russian Foundation for Basic Research (grant nos. 10-08-90421-Укр and 10-03-00466-a) and the grant of the President of the Russian Federation MD-5551.2010.3. ru Інститут проблем матеріалознавства ім. І.М. Францевича НАН України Наноструктурное материаловедение Наночастицы, нанокластеры, нульмерные объекты Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix Article published earlier |
| spellingShingle | Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix Lashkarev, G.V. Demydiuk, P.V. Yurkov, G.Yu. Dmitriev, O.I. Bykov, O.I. Klochkov, L.I. Pyratinskiy, Y.P. Slynko, E.I. Khandozhko, A.G. Popkov, O.V. Taratanov, N.A. Наночастицы, нанокластеры, нульмерные объекты |
| title | Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix |
| title_full | Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix |
| title_fullStr | Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix |
| title_full_unstemmed | Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix |
| title_short | Properties of nanoparticles ZnO:Mn immobilized in polyethylene matrix |
| title_sort | properties of nanoparticles zno:mn immobilized in polyethylene matrix |
| topic | Наночастицы, нанокластеры, нульмерные объекты |
| topic_facet | Наночастицы, нанокластеры, нульмерные объекты |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/62735 |
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